Food products coated with 1, 6-GPS and 1, 1-GPM

ABSTRACT

The invention concerns improved sugar-free products, their production and use, in particular, coated products, their production and use. The products are characterized by their content in enriched mixtures of 1-O-α-D-glucopyranosyl-D-mannitol (1,1-GPM) and 6-O-α-D-glucopyranosyl-D-sorbitol (1,6-GPS).

CROSS-RELATED APPLICATION

This is a continuation of application Ser. No. 09/030,295 filed Feb. 25,1998 and now abandoned, which was a continuation of International PatentApplication PCT/EP96/03740, filed Aug. 24, 1996.

DESCRIPTION

The invention under consideration concerns improved sugar-free products,their production and use, in particular, coated products, theirproduction and use.

Coated products contain a coating produced from sugar, sugar alcohols,chocolates, and/or other glazes with a liquid, soft, or solid core.Chewing gum inserts, frufts, compressed material, or otherpharmaceutical products are, for example, used as cores. Thus, forexample, U.S. Pat. No. 4,792,453 describes a sugar-free coated chewinggum, whose coating contains hydrogenated isomaltulose. This chewing gumis obtained by coating with a syrup which contains the hydrogenatedisomaltulose. Thus, 1-O-α-D-glucopyranosyl-D-mannitol (1,1-GPM) and6-O-α-D-glucopyranosyl-D-sorbitol (1,6-GPS), dissolved in approximatelyequimolar quantities, are present in the syrup coating.

A number of methods for the production of coated products are alsoknown. Essentially, a distinction is made between soft coating, hardcoating, and suspension dragee formation. Soft coating means theapplication of saccharides dissolved in water on cores which are moving,wherein after each application, saccharide powder is sprinkled, so as tobind the moisture. This type of coating forms a soft dragée coating(European Patent No. 1,625,311 A1). The fact that the metering of thesyrup used for the coating—that is, the dissolved saccharide—and themetering of the powder must be coordinated with one another proves to bea disadvantage, in addition to the complicated processing execution.

Hard coating is likewise understood to mean—just as with softcoating—the application of saccharides dissolved in water on cores whichare moving, wherein, however, saccharide powder is not applied, butrather the nonaqueous components are immediately dried. As with softcoating, a large number of different individual applications (50-120)are carried out, between which drying is undertaken with warm or coldair, so that various thicknesses of dragée coatings can be produced.Also, hard coating methods with two different saccharide solutions,which are applied after one another (“dual-composition coating”), arealso known. Thus, in more recent times, methods are described in whichmaltitol-containing layers are first applied and then the remainingcoating was built up with xylitol (U.S. Pat. No. 5,376,389). Thesemethods, however, use two different saccharides for the production ofthe solution to be applied and accordingly, have to be carried out in acomplicated manner. In addition, coating layers made of xylitol detachreadily during the coating process, in particular on the corners andedges of the coated cores.

Both in hard coating as well as in soft coating methods, the problem ofthe adhesion tendency upon application of the aqueous solutionsarises—for example, when using hydrogenated isomaltulose for thecoating. This adhesion tendency causes the coating material to sticktogether or a sticking to the walls of the container used for thecoating.

A third possibility for coating is to be found in the use of asuspension. The suspended mixture used up to now—for the most part onlywith sugar-containing products—consists of a liquid phase (which, forexample, contains sugar, rice starch, and glucose dissolved in water)and a solid phase which consists of fine, crystalline sugar particles.The separate use of various sucroses is characteristic of this type ofsuspension-coating.

The coating products obtained with the described methods tend to losetheir crispiness during storage because of the composition of theircoating and their core. The reason for this is apparently to be found inthe diffusion of moisture from the core into the coating. In the longrun, this process also leads to undesired drying out of the dragée core.Conversely, the known products exhibit an undesired water absorption ina moist warm atmosphere, whose results are sticky, soft products, whichare thus unattractive for consumption.

Also the products which are not coated and have been known up to now inthe state of the art are capable of improvement with regard to theirstorage capacity, sweetening power, or solubility. These disadvantagesoriginate in the type and composition of the saccharides used for theproduction of the products or their mixtures, such as hydrogenatedisomaltulose. Hydrogenated isomaltulose is formed by the hydrogenationof isomaltulose and contains the components6-O-α-D-glucopyranosyl-D-sorbitol (below, referred to as 1,6-GPS) and1-O-α-D-glucopyranosyl-D-mannitol (referred to below as 1,1-GPM) in aratio of approximately 1:1. Hydrogenated isomaltulose is dissolved onlymoderately in water, and in dissolved form tends to adhere uponapplication to the surfaces involved in the coating.

The technical problem at the core of the invention under considerationthus is to make available products which overcome the aforementioneddisadvantages, methods for their production, and their use.

The solution to this technical problem is to be found in makingavailable the saccharide mixtures characterized in the patent claims,products containing these mixtures, methods for their production, andtheir use in the food area, in particular, the sweetener andpharmaceutical areas.

In particular, the invention makes available 1,6-GPS-enriched mixtures,consisting of 1,6-GPS and 1,1-GPM, in a ratio of 57:43 wt %, inparticular greater than 57:less than 43 wt %, to 99:1 wt % (based on thedry substance of the mixture of 1,6-GPS and 1,1-GPM, used forproduction, wherein its 1,6-GPS/1,1-GPM content is equal to 100%) and1,1-GPM-enriched mixtures, consisting of 1,6-GPS and 1,1-GPM, in a ratioof 1:99 wt % to 43 wt %:57 wt %, in particular, smaller than 43:greaterthan 57 wt % (based on the dry substance of the mixture of 1,6-GPS and1,1-GPM, used for production, wherein its 1,6-GPS/1,1-GPM content isequal to 100%). Depending on the composition of the starting substanceused for their production, the mixtures can also contain smallquantities of sorbitol, mannitol, etc. The mixtures in accordance withthe invention can be used in a particularly advantageous manner insolution or as a suspension for the coating of products in the sweeteneror pharmaceutical areas. In accordance with the invention, the mixturescan comprise an additive, an essential component, or essentially a solecomponent of the most varied products in the food or pharmaceuticalareas. The 1,6-GPS- and 1,1-GPM-enriched mixtures in accordance with theinvention can be, particularly advantageously, produced from a singlebasic substance, namely hydrogenated isomaltulose. Therefore, inaccordance with the invention, it is possible to produce two mixtures,each with different characteristics, from this commercially obtainablebasic substance. The 1,6-GPS-enriched mixture is characterized by anincreased solubility and greater sweetening power, in comparison tohydrogenated isomaltulose and the 1,1-GPM-enriched mixture. The greatersweetening power is based, on the one hand, on the fact that 1,6-GPSgoes into solution more rapidly and thus triggers a more rapid sweetsensation and, on the other hand, on the objectively greater sweeteningpower which is characteristic of the compound 1,6-GPS. The1,1-GPM-enriched mixture exhibits a lower solubility than hydrogenatedisomaltulose. The deliberate use of these two substances in products inthe food, sweetener, or pharmaceutical areas makes it possible to impartto the products an improved storage stability and greater sweeteningpower and to simplify their production method.

The invention concerns, in particular, coated products, comprising acore and a coating, wherein the coating contains at least one layer madeof a 1,6-GPS-enriched mixture, consisting of 1,6-GPS and 1,1-GPM, in aratio of 57:43 wt %, in particular, greater than 57:smaller than 43 wt%, to 99:1 wt % (based on the dry substance of the mixture of 1,6-GPSand 1,1-GPM, used for production, wherein its 1,6-GPS/1,1-GPM content isequal to 100%) and/or of a 1,1-GPM-enriched mixture, consisting of1,6-GPS and 1,1-GPM, in a ratio of 1:99 wt % to 43:57 wt %, inparticular, smaller than 43:greater than 57 wt % (based on the drysubstance of the mixture of 1,6-GPS and 1,1-GPM, used for production,wherein its 1,6-GPS/1,1-GPM content is equal to 100%). This/theselayer(s) comprise(s) either exclusively—perhaps with the inclusion ofimpurities resulting from the starting substance, such as sorbitol ormannitol—the mixtures in accordance with the invention or thecompositions containing the mixtures in accordance with the invention.The coated products, in accordance with the invention, contain either acore of known composition or a core which comprises one or two of the1,6-GPS- or 1,1-GPM-enriched mixtures, in accordance with the invention,and a coating of at least one layer of one of the mixtures in accordancewith the invention—that is, at least one layer of the 1,1-GPM- or1,6-GPS-enriched mixture.

In a particularly preferred specific embodiment of the invention, thecoated products exhibit at least one and preferably 25-45 layers of the1,6-GPS- and 1,1-GPM-enriched mixture. The thus coated products aresheathed by layer sequences with different compositions. By selectingthe series sequence and the number of coating steps with the variousmixtures, it is possible to deliberately produce products with desiredcharacteristics. In accordance with the invention, provisions can bemade so that the core is first sheathed with, in total, 25-45 layers ofthe 1,1-GPM-enriched mixture and then on these layers, other, inparticular 25-45, layers of the 1,6-GPS-enriched mixture are applied.Such a structured coated product is characterized, as a whole, by ahigher sweetening power, in comparison to traditional products coatedwith hydrogenated isomaltulose, as a result of the higher solubility andgreater sweetening power of the 1,6-GPS-enriched mixture forming theouter layers. Another advantage is found in the presence of the1,1-GPM-enriched layer sequence between the core and outer layer, whichprevents a diffusion of moisture to the surface of the dragée because ofits lower solubility, in comparison to traditional hydrogenatedisomaltulose. The products therefore exhibit an improved crispiness andlonger storage stability. In addition and conversely, in the moist, warmatmosphere, less moisture penetrates from the surroundings into thecore, so that the storage stability is improved even under thesecircumstances. The invention, however, also comprises an embodiment inwhich the layers close to the core are constituted from the1,6-GPS-containing mixture, whereas the outer layer contains the1,1-GPM-enriched mixture.

In the pharmaceutical field also, the solubility of products or, in thecase of coated products, the solubility of their coatings, frequentlyplays a role. The solubility of the products or coatings directlyinfluences the active-ingredient release and thus also the active siteand the active time of the applied pharmaceuticals. In cases in which amore rapid release of the pharmaceuticals is desired, only, orpredominantly, 1,6-GPS-enriched mixtures with their increased solubilityare used, in accordance with the invention, as the coating or for theproduction of the drug carrier. Conversely, in cases in which a sloweractive-ingredient release is desired, only, or essentially, a1,1-GPM-enriched mixture can be used for the production of the coatingor the drug carrier.

The invention also concerns a method for the production of a coatedproduct, which is characterized in that at least once a solution orsuspension of the 1,6-GPS-enriched mixture and/or sometime before orsubsequently, a solution or suspension of the 1,1-GPM-enriched mixtureis applied on the core and the solvent is evaporated before theapplication of each layer. The method in accordance with the inventionprovides for either a solution or, particularly preferably, a suspensionof one of the mixtures in accordance with the invention being applied atleast once on a core. A multiple application is particularly preferredso that the coating comprises several layers. Particularly preferred isa method in which layers of the two mixtures in accordance with theinvention are applied, one after another, on the core. A specificembodiment of the invention provides for 25-45 applications of thesolution or suspension of the 1,1-GPM- and 1,6-GPS-enriched mixture tobe carried out. Depending on the desired characteristics of the coatedproduct, for example, the layers which contain the 1,1-GPM-enrichedmixture are applied; they are then covered by 1,6-GPS-enriched layers.The invention, however, also comprises the application of1,6-GPS-enriched layers first, followed by the application of1,1-GPM-enriched layers. After the application of each layer, thesolvent is evaporated, preferably with a gas flow which has a dew pointof −15o to +10° C., with 0° C. being particularly preferable. Theapplication of the suspension or solution is carried out whilemaintaining a constant temperature and while avoiding water losses. Thiscan, for example, take place fully automatically in a DRIACOATER 1200from the Driam Company, Eriskirch, wherein the suspension is sprayed onwith a diameter of 1.5-2.0 mm, using Schlick fan nozzles.

In a preferred embodiment of the invention, the mixtures in accordancewith the invention, in particular, the coating of the coated productscontaining these mixtures, also contain gum arabic in a quantity of0.5-10 wt %, based on the dry substance of the coating. In accordancewith the invention, the coating comprises 10-90 wt %, in particular,25-35 wt % of the dry substance of the coated products. The mixtures inaccordance with the invention and in particular, the coating of thecoated products made from such mixtures can contain dyes, in particular,titanium dioxide.

In another specific embodiment of the invention, the mixtures andtherefore also the coating have, moreover, one or more sugarsubstitutes, in particular, xylitol, mannitol, sorbitol, maltitol,lactitol, or erythritol. The invention also provides for the mixtures orthe coating to also be able to contain fillers, in particular,polydextrose, calcium carbonate, or inulin.

The invention under consideration also comprises mixtures and coatingscontaining these mixtures, surfactant substances, such as polysorbates(ethoxylated sorbitan esters), in particular, in a quantity of 0.05-0.5wt %, and/or film-forming agents, such as methylcellulose gelatin,hydroxypropyl cellulose, ethylcellulose, hydroxyethylcellulose,carboxymethylcellulose, and mixtures thereof. In addition, binders, suchas alginates, plant gums, or plasticizers, can also be present.

In another specific embodiment, the invention concerns the mixtures inaccordance with the invention and the mixture-containing coatings ofcoated products which contain intensive sweeteners, in particular,cyclamate, saccharin, aspartame, glycyrrhizin, dihydrochalcone,thaumatin, monellin, acesulfame, alitam, or sucralose.

In particular, the invention concerns a coated product, whose core is achewing gum cushion, a chewing gum ball, a fruit, nut, bean-shapedchocolate, hard caramel, soft caramel, jelly, gum arabic product,nonpareil, small sugar bead, a snack, pharmaceutical product, or anotherlumpy food product.

The core can be of a known nature or contain a 1,6-GPS- or1,1-GPM-enriched mixture of 1,6-GPS and 1,1-GPM. Of course, theinvention can provide for this core to also contain the dyes, binders,sugar substitutes, intensive sweeteners, surfactants, or fillers. Theinvention also comprises a coated product with a core in the form of acompressed material. The compressed material can contain 1,6-GPS- or1,1-GPM-enriched material or be a compressed material of the twomixtures. The selection and quantity of the mixture used for thiscompressed material in accordance with the invention influences itssolubility and thus perhaps the pharmaceuticals contained in thecompressed material also.

The invention also makes available a method for the production of a1,6-GPS- and a 1,1-GPM-enriched 1,6-GPS- and 1,1-GPM-containing mixtureof a single starting substance, namely hydrogenated isomaltulose, whichis characterized in that hydrogenated isomaltulose is dissolved inwater, crystalline hydrogenated isomaltulose is added in a quantity sothat its solubility is exceeded, the formed suspension is filtered, andthe 1,6-GPS-enriched filtrate is separated from the 1,1-GPM-enrichedfilter cake, or hydrogenated isomaltulose is mixed with water in such aratio that the water quantity is not sufficient at the selectedtemperature so as to dissolve the entire quantity of isomalt mixture(see FIGS. 7 and 8).

Therefore, this method is characterized in that for the production ofthe two mixtures in accordance with the invention, merely one startingsubstance—namely, hydrogenated isomaltulose—is used. Hydrogenatedisomaltulose can be obtained under the trade names Palatinit^(R) orISOMALT^(R) from the Palatinit Company, Mannheim. It contains more than98% 1,6-GPS and 1,1-GPM, wherein admixtures of sorbitol or mannitol arepossible. In connection with the invention under consideration,concentrations of 1,6-GPS and 1,1-GPM always refer to the used quantityof 1,6-GPS and 1,1-GPM equal to 100%. In accordance with the invention,a saturated solution, for example, of ISOMALT^(R) Type M, is produced ata temperature of 20°-95°. As a function of the temperature used, solid,powdery hydrogenated isomaltulose, for example, ISOMALT^(R) Type PF(powder), is added at this temperature and this is done in such aquantity that the solubility described in FIG. 6 is exceeded by 1-40%.The crystalline, hydrogenated isomaltulose which is added to the aqueoussolution of hydrogenated isomaltulose, therefore, experiences conditionsunder which a complete solution of the hydrogenated isomaltulose is nolonger possible. A suspension is therefore formed. The total solidscontent of this suspension can thereby be approximately 50-90 wt %,wherein the solids are present partially dissolved and partiallyundissolved. In the production of the suspension, the mixture ispreferably stirred well. The establishing of an equilibrium between thecomposition of the liquid and the solid phases of the suspension dependson the total solids fraction and the temperature and is completed afterapproximately 10-60 min. After the establishing of this equilibrium, aliquid phase is present which contains 1,6-GPS and 1,1-GPM in a ratiodifferent from that in hydrogenated isomaltulose. The suspended, solidphase also contains 1,6-GPS and 1,1-GPM in a ratio different from thatin hydrogenated isomaltulose. Moreover, 1,1-GPM is present in the solidphase in contrast to the 1,1-GPM in the liquid phase as a dihydrate. Thecomposition of the liquid and the solid phases—that is, the quantitativeratios of 1,6-GPS to 1,1-GPM—can be adjusted in broad limits, inaccordance with the invention—this can be done by means of thetemperature of the suspension and the relatively undissolved solidsfraction. FIGS. 1-5 illustrate that the composition of the phasesobtained and thus of the mixtures in accordance with the invention canbe regulated in a deliberate manner by adjusting the temperature and therelatively undissolved solids fraction. The total ratio (dissolved andsolid) of 1,6-GPS to 1,1-GPM contained in the two phases corresponds, ofcourse, to that of the used, hydrogenated isomaltulose. A lowundissolved solids fraction in the suspension produces a high1,1-GPM-dihydrate concentration in the solid phase, a high undissolvedsolids fraction, but a composition similar to that of the hydrogenatedisomaltulose, wherein, however, 1,1-GPM-dihydrate is concentrated in thesolid phase. In the solid phase, therefore, 1,1-GPM is alwaysconcentrated, wherein the ratio of 1,6-GPS to 1,1-GPM can vary from 1:99wt % to 43:57 wt %, in particular smaller than 43:larger than 57 wt %.In the liquid phase, 1,6-GPS is always concentrated, wherein the ratioof 1,6-GPS to 1,1-GPM can vary from approximately 57:43 wt %, inparticular, greater than 57:smaller than 43 wt %, to 99:1 wt %.

In accordance with the invention, the suspensions containing the twophases can also be produced by cooling supersaturated solutions ofhydrogenated isomaltulose and a spontaneous or induced fine-grainformation, perhaps by the addition of inoculation crystals orISOMALT^(R) PF or PE.

After the equilibrium has been established by adjusting the temperatureand the relatively undissolved solids fraction in the desired manner,the two phases are separated from one another in accordance with theinvention. The separation of the two phases provided for in accordancewith the invention takes place by filtering, centrifuging orsedimentation, but can also take place by means of other method steps. A1,1-GPM-enriched solid phase and a 1,6-GPS-enriched liquid phase, eachof which comprises 1,6-GPS and 1,1-GPM in different quantitative ratios,are obtained. The liquid phase can be converted into a solid phase byevaporating.

The method in accordance with the invention accordingly makes possiblethe preparation of 1,6-GPS-enriched mixtures, consisting of 1,6-GPS and1,1-GPM, in a ratio of 57:43 wt %, in particular, greater than 57 wt%:smaller than 43 wt %, to 99:1 wt %. The invention also makes available1,1-GPM-enriched mixtures, consisting of 1,6-GPS and 1,1-GPM, in a ratioof 1:99 wt % to 43:57 wt %, in particular, smaller than 43 wt %:greaterthan 57 wt %. These mixtures can, for example, be used in the form oftheir solution to make dragées. A suspension can also be used instead ofa solution. The use of a suspension of hydrogenated isomaltulose andparticularly preferred in accordance with the invention, a suspension of1,6-GPS- or 1,1-GPM-enriched mixtures for the formation of coatedproducts has the advantage of a strongly reduced adhesion tendencyduring the coating. Moreover, the application of highly dry substancecontents in a relatively short drying time is possible, sinceundissolved solids, together with dissolved components, are applied onthe dragée material. The advantageous, reduced adhesion tendency isbased on the presence of very high fractions of crystallization nuclei,which consist of 1,1-GPM-dihydrate and 1,6-GPS.

The deliberate use of the different compositions and the relateddifferent characteristics of the mixtures in accordance with theinvention permits not only the production of improved, glazed productsor compressed materials, but of course, also the production of improvedproducts in all areas in which sugar or sugar substitutes play a role.In accordance with the invention, for example, the 1,6-GPS-enrichedmixture can be used as the soft filling in soft caramels. The1,6-GPS-enriched mixture can also replace the previously used, verysoluble sugar substitutes, such as maltitol, in the aforementionedproducts. Hard caramels can, in accordance with the invention beproduced by using the 1,1-GPM-enriched mixtures. The products containingthe mixtures in accordance with the invention, in particular, the glazedproducts or the coated products, can be composed by the suitableselection of the composition of the used mixtures and layer sequence sothat the total composition of the 1,6-GPS and 1,1-GPM contained in theproduct corresponds to the composition in commercial hydrogenatedisomaltulose (ISOMALT^(R), Palatinit^(R)).

One specific embodiment of this invention makes available a productwhich comprises at least one of the mixtures enriched by 1,6-GPS and1,1-GPM in accordance with the invention. These products can alsocontain gelatin, fat or fat substitutes. They can, of course, alsocontain the already mentioned fillers, binders, dyes, intensivesweeteners, emulsifiers, surfactants, sugar substitutes, othersweeteners, or pharmaceutical active ingredients.

The invention concerns, in particular, products which take the form of ahard caramel, soft caramel, gelatin product, chocolate, chocolate kiss,chewing gum cushion, chewing gum strip, foam sugar goods, baked goods,cookies, coated products or medication.

The mixtures in accordance with the invention can be polymerized in anadvantageous manner with the monomers of known plastics, for example,polyurethane, and form addition polymers which can be used in the mostvaried areas, such as plastics technology or pharmacy.

In particular, the invention concerns a product which takes the form ofa compressed material. In accordance with the invention, compressedmaterials can, for example, contain the compressed, solid1,1-GPM-enriched phase of the mixture in accordance with the invention.A compressed material, in accordance with the invention, which containsthe 1,6-GPS-enriched mixture obtained by evaporation from the liquid1,6-GPS enriched phase, is also preferred. The compressed materials areparticularly suitable for inclusion of drugs and their application. Theycan, for example, be in the form of tablets which are sucked or chewed.

The invention also provides for the production of the compressedmaterials from the two mixtures in accordance with the invention.Depending on the composition of the two individual mixtures and therelative fraction of these individual mixtures in the compressedmaterial, it is possible to establish desired solubility characteristicsin a controlled manner.

The figures show the following:

FIG. 1 represents the composition of the 1,6-GPS- and 1,1-GPM-enrichedphases, which are obtained from a suspension, heated to 70° C., with adry substance fraction of 75 wt %.

FIG. 2 represents the composition of the 1,6-GPS- and 1,1-GPM-enrichedphases, which are obtained from a suspension, heated to 70° C., with adry substance fraction of 80 wt %.

FIG. 3 represents the composition of the 1,6-GPS- and 1,1-GPM-enrichedphases, which are obtained from a suspension, heated to 60° C., with adry substance fraction of 75 wt %.

FIG. 4 represents the composition of the 1,6-GPS- and 1,1-GPM-enrichedphases, which are obtained from a suspension, heated to 60° C., with adry substance fraction of 65 wt %.

FIG. 5 represents the composition of the 1,6-GPS- and 1,1-GPM-enrichedphases, which are obtained from a suspension, heated to 50° C., with adry substance fraction of 70 wt %.

FIG. 6 represents the solubility of hydrogenated isomaltulose(ISOMALT^(R)) in water.

FIG. 7 represents the connection between the dry substance content(B×value) of a solution saturated with hydrogenated isomaltulose(=ISOMALT^(R)) and the starting concentration of hydrogenatedisomaltulose in water at different temperatures.

FIG. 8 represents the connection between the ratio of 1,6-GPS and1,1-GPM in a solution saturated with hydrogenated isomaltulose and thestarting concentration of hydrogenated isomaltulose in water atdifferent temperatures.

FIG. 9 represents the dissolution kinetics of compressed materialsconsisting of 1,6-GPS and 1,1-GPM.

FIG. 10 represents the dependence of the weight change of hard caramelson their composition of 1,6-GPS and 1,1-GPM.

EXAMPLE 1

Production of 1,1-GPM- and 1,6-GPS-enriched 1,1-GPM/1,6-GPS Mixtures at70° C. (with the Addition of Gum Arabic)

1920 g ISOMALT^(R) Type M (hydrogenated isomaltulose) and 67.5 g gumarabic (rapidly soluble) are dissolved in 670.8 g water at 80° C. andsubsequently cooled to 70° C. While stirring, 341.7 g ISOMALT^(R) PF(powder) are added. The water content of 3.5 wt % in ISOMALT^(R) wastaken into consideration thereby.

After 60 min, the solid phase is separated from the liquid phase. Thiscan occur, for example, by centrifugation or filtration.

In the example under consideration, the separation of the solid phasefrom the liquid phase is undertaken by filtration via a pressure filtertempered to 70° C. after 20, 60, 120, and 180 min. The compositions ofthe obtained phases are represented in Table I, below:

TABLE 1 Sample 1 2 3 4 Filtrate in g 85.85 100.89 130.83 100.9 Filtercake (moist) 37.76 51.55 54.76 32.34 Filter cake (dry) 34.30 48.56 52.1029.53 Filtrate 75.1:24.9 76.7:23.3 77:23 74.5:25.5 (1,6-GPS:1,1-GPM)%(1,6-GPS:1,1-GPM)% 61:39 66.5:33.5 67.6:32.4 67.2:32.8 Solid

The results are shown in FIG. 1 in graphical form.

After 60 min, 1,6-GPS has been concentrated to approximately 75% in theliquid phase, whereas in the solid phase, 1,1-GPM (calculated withoutwater of hydration) has been concentrated to more than 65%.

The liquid phase can be converted into suspension form or into the solidphase by evaporating or reducing the temperature.

By repeating this suspension-separation method with the individuallyobtained phases, 1,6-GPS or 1,1-GPM is obtained in pure form. It is alsopossible, in accordance with the invention, to obtain1,1-GPM/1,6-GPS-enriched mixtures of a desired composition by theselection of suitable temperatures and concentrations of hydrogenatedisomaltulose and perhaps a repetition of the separation process severaltimes.

EXAMPLE 2

Production of 1,1-GPM- and 1,6-GPS-enriched 1,1-GPM/1,6-GPS Mixtures at35° C.

5 kg Isomalt^(R) are added to 5 kg water (fully deionized). Thesuspension is stirred at 35° C. for 1-20 h, depending on the grain size.

Subsequently, this suspension is separated into the liquid and solidphases in a heated pressure filter at 35° C.

The clear solution is evaporated and dried in a rotary evaporator,perhaps subsequently comminuted.

1.95 kg white solid are obtained (water content before drying 24.8%,1,1-GPM:1,6-GPS ratio 84:16%) and 7.86 kg clear solution (42.3° Brix,1,1-GPM:1,6-GPS ratio 33.5:66.5%).

The separation of the two phases can take place also by means of avacuum filter, centrifuge or by sedimentation.

Examples 1 and 2 and FIGS. 1-5 illustrate that with a deliberate use ofthe reaction parameters, temperature and solids concentration, it ispossible to obtain mixtures of a desired composition.

FIGS. 7 and 8 illustrate this advantage in accordance with theinvention.

From these figures one can see at what ratio hydrogenated isomaltulose(ISOMALT^(R)) is mixed with water and at what temperature thissuspension must be maintained, so as to obtain a liquid phase with acertain 1,6-GPS:1,1-GPM ratio, for example.

If, for example, ISOMALT^(R) is mixed with water at a ratio of 2:1, thenan approximately 57° Brix solution with a 1,6-GPS:1,1-GPM ratio of77:23%, i.e., 3,3:1 is obtained at a temperature of 45° C.

The same mixture, however, leads to an approximately 59° Brix solutionwith a 1,6-GPS:1,1-GPM ratio of 67:33%, i.e. 2:1, at 55° C.

EXAMPLE 3

Production of Coated Products in the Hard Coating Process

Recipe: 1,1-GPM-enriched mixture (85% GPM, 15% GPS) 30 kg Gum arabic1.25 kg Titanium dioxide 0.5 kg Water 18.3 kg

Production of the Coating Solution and the Coating Process

The 1,1-GPM-enriched mixture and gum arabic are dissolved in water atapproximately 85° C., cooled to 70° C., and then titanium dioxide issuspended therein.

This mixture is maintained at 70° C., while stirring, and applied onchewing gum cushions (approximately 50-80 individual applications) in ahard coating process.

The chewing gum inserts (60 kg) are moved in a Diacoater 1200 (DriamCompany, Eriskirch) and dried with air (temperature 25° C., dew point 0°C.) in a counterflow method after each application, for 2-5 min.

The advantage of the used sugar-free raw material (1,1-GPM-enrichedmixture) is to be found particularly in the fact that due to the lowsolubility of the 1,1-GPM-dihydrate formed on the cores, a barrier layeris formed around the core, which prevents the diffusion of water andother volatile fractions (flavors) from the core. In this way, there isno drying out, as is frequently observed with other dragées. Also thesensorically determinable crispiness is maintained for a longer periodof time.

EXAMPLE 4

Production of Coated Products in the “Dual Composition” Process

Recipe I: 1,1-GPM-enriched mixture (85% 1,1-GPM, 15% 1,6-GPS) 15 kg Gumarabic 0.6 kg Titanium dioxide 0.25 kg Water 9.5 kg Recipe II:1,6-GPS-enriched mixture 77% 1,6-GPS, 23% 1,1-GPM) 16 kg Gum arabic 0.6kg Titanium dioxide 0.25 kg Water 7.75 kg

Methods

Recipe I is produced as described in Example 3 and sprayed on thechewing gum inserts, wherein half of the dragée coating (layers directlyon the core) is applied in 45 individual applications.

Recipe II is produced as in recipe I, wherein, however, the temperatureof the mixture is 60° C. In 35 individual applications, this suspensionis brought up to the desired dragée end weight on the chewing guminserts coated with recipe I.

The experimental parameters correspond to those of Example 3.

The hard-to-dissolve 1,1-GPM-dihydrate from recipe I (see also Example3) forms a barrier layer against moisture from the core. The1,6-GPS-enriched outer layer influences the sweet sensation in apositive manner, as is shown by sensory investigations (threshold valuedeterminations, differentiation testing in pairs).

EXAMPLE 5

Production of Coated Products in the Suspension Method

Recipe 1,6-GPS-enriched mixture (73% 1,6-GPS, 27% 1,1-GPM) 43.6 kg Water29 kg Acesulfame K 0.05 kg Aspartame 0.05 kg Titanium dioxide 1.0 kg Gumarabic 2.05 kg 1,6-GPS-enriched mixture (powder, 77% 1,6-GPS, 24.25 kg23% 1,1-GPM)

Production of the Suspension

While stirring, 1,6-GPS-enriched mixture (43.6 kg) and gum arabic aredissolved in water and the solution is heated to 75° C., until acrystal-free solution is present; this solution is cooled toapproximately 60° C.; aspartame, acesulfame K, titanium dioxide, and1,6-GPS-enriched mixture (powder) are added until a homogeneous mass ispresent. The temperature of the suspension is regulated to 55° C. andretained during the process.

The coatings are formed in a manner analogous to the method describedunder Example 3. A highly dry substance application per unit time isproduced. Among other things, a more rapid sweet sensation duringconsumption is perceived by the increased solubility of 1,6-GPS.

EXAMPLE 6

Production of Chewing Gum (Strips) Containing a 1,6-GPS-enriched and a1,1-GPM-enriched 1,1-GPM/1,6-GPS Mixture

Recipe Chewing base Nostic TWA 1.5 kg 1,6-GPS-enriched mixture (76.5%1,6-GPS, 23.5% 1,1-GPM) 2.0 kg Sorbitol syrup (70% dry substance) 0.6 kg1,1-GPM-enriched mixture (85% 1,1-GPM, 15% 1,6-GPS) 0.5 kg Glycerol 0.15kg Menthol 0.15 kg Flavor (Spearmint) 0.1 kg Aspartame 2.5 g AcesulfameK 2.5

Production

The chewing gum base is heated at approximately 55° C. in a heatingoven, before it is placed in a kneader; subsequently, the chewing gumbase is kneaded for 1-2 min. During the kneading, the powdery additives(1,1-GPM- and 1,6-GPS-enriched mixture, sweetener, menthol) aregradually added in the indicated sequence; afterwards flavor, sorbitolsyrup, and glycerol are added. The kneading continues until the mass ishomogeneous (end temperature, approximately 45° C.). The mass is takenfrom the kneader and divided into portions which weigh approximately 1kg.

The chewing gum mass divided into portions is placed in intermediatestorage for approximately 15-20 min on a talc-strewn substrate, extrudedwith a suitable extruder, and further processed as usual.

The extensive replacement of the readily soluble sugar alcohol sorbitoland the complete replacement of the likewise readily soluble maltitol bythe less-soluble sugar alcohols 1,6-GPS and 1,1-GPM leads to theso-called “long-lasting” effect (flavor reinforcement).

The product is particularly suitable for diabetics also.

EXAMPLE 7

Production of Soft Caramels (Fruit Flavor) Containing a 1,6-GPS-enrichedand a 1,1-GPM-enriched 1,1-GPM/1,6-GPS Mixture

Recipe 1,6-GPS-enriched mixture (67% 1,6-GPS, 33% 1,1-GPM) 24 kgRaftilose L95 (80% dry substance, 51 kg fructooligosaccharide) Water 5kg Gelatin 120 Bloom (40%) 3.6 kg Vegetable fat (34-36° Sp) 6.0 kgEmulsifier 0.8 kg Citric acid (monohydrate) 0.7 kg 1,1-GPM-enrichedmixture (85% 1,1-GPM, 15% 1,6-GPS) 8 kg Flavor (lemon) 0.1 kg

Production

The 1,6-GPS-enriched mixture, Raftilose L95, and water are boiled in abatch boiler to 132-136° C.(depending on the desired consistency); thegelatin solution, vegetable fat, emulsifier, citric acid, and1,1-GPM-enriched mixture are added in the indicated sequence and mixedat a high speed for 2-3 min, until a homogeneous mass is formed.Finally, flavor is added and the vessel is emptied. Homogenizing with asuitable homogenizer (Homozenta) is advantageous. The soft caramel mass,cooled to 44-46° C., is then drawn for 5-10 min (temperature is then47-49° C.).

In contrast to the common sugar-free soft caramels, the product producedabove contains only diabetic-suitable additives.

EXAMPLE 8

Production of Hard Caramels Containing a 1,1-GPM-enriched1,1-GPM/1,6-GPS Mixture

Recipe 1,1-GPM-enriched mixture (85% 1,1-GPM, 15% 1,6-GPS) 25 kg Water 8kg Citric acid 0.3 kg Flavor (pineapple) 0.1 kg Acesulfame K 25 g

Production

The 1,1-GPM-enriched mixture and water are boiled in a candy boiler to155-160o, exposed to a full vacuum for 5 min, and after cooling the massto 110-115° C., acid, flavor, and sweetener are added. Subsequently, themass is given the shape of candies and cooled.

Alternately, the recipe above can be processed directly to candies,without the addition of water, in a melt extrusion process. The meltextrusion process can, of course, also be used if hard caramels areproduced from the 1,6-GPS-enriched mixture.

1,1-GPM-enriched hard caramels form a microcrystalline boundary layer of1,1-GPM-dihydrate on the surface, which leads to a reduced stickinessand reduces the further water intake from the atmosphere (favorablestorage behavior). The products are suitable for diabetics.

Moreover, 1,1-GPM-enriched hard caramels exhibit an increasedtemperature stability. The temperature stability is described by theglass-transition temperature Tg°C.—that is, 1,1-GPM-enriched hardcaramels have a high glass-transition temperature (Tg=65.6° C. +/−1.8°C., in comparison to IsomaltR hard caramels Tg=57.5° C.+/−1.7° C.).

EXAMPLE 9

Production of a Compressed Material of 1,1-GPM- and 1,6-GPS-enriched1,1-GPM/1,6-GPS Mixtures

Recipe Fruit flavor Mint flavor a) 1,1-GPM-enriched mixture 9.9 kg 9.9kg  (85% 1,1-GPM, 15% 1,6-GPS) b) 1,6-GPS-enriched mixture 9.9 kg 9.9 kg (83% 1,6-GPS, 17% 1,1-GPM) Acesulfame K 15 g 15 g Citric acid 30 g —Flavor 50 g 50 g Magnesium stearate 50 g 50 g Production of tablets forsucking (tablets for chewing)

The components are mixed and pressed in an eccentric press under thefollowing conditions:

Force of pressure 20-70 kN Specific force of pressure 0.2-0.9 kN/mm²

For tablets for sucking, a) 1,1-GPM-enriched mixture is used; b)1,6-GPS-enriched mixture is used for tablets for chewing.

A slow dissolution and thus a prolonged release of flavor or activeingredients with compressed pharmaceutical materials is brought about asa result of the low solubility of the 1,1-GPM-enriched mixture. FIG. 9illustrates the lower solubility of a 1,1-GPM-enriched compressedmaterial in comparison to a 1,6-GPS-enriched compressed material. The1,6-GPS-enriched compressed materials were compressed withoutauxiliaries under 70 kN; the 1,1-GPM-enriched compressed materials,under 50 kN, also without auxiliaries.

EXAMPLE 10

Production of Filled Hard Caramels, wherein the Shell of the1,1-GPM-enriched Mixture and the Liquid Filling Contain 1,6-GPS-enrichedMixture

1. Hard Caramel Mass

1,1-GPM-enriched mixture (85% 1,1-GPM, 15% 1,6-GPS) 25 kg Water 8 kgCitric acid 0.3 kg Lemon flavor 0.03 kg

Production

The 1,1-GPM-enriched mixture and water are boiled in a candy boiler at155-160° C., exposed to a full vacuum for 5 min, and subsequently, acidand flavor are added. The melt is cooled to 65-70° C. in a taperedroller.

2. Filling

Recipe Raftilose L95 (fructooligosaccharide) 2.5 kg 1,6-GPS-enrichedmixture (82% 1,6-GPS, 18% 1,1-GPM) 5.9 kg Water 1.5 kg Citric acid 0.09kg Lemon flavor 0.01 kg

Production

Raftilose L95 is heated to 80° C. with water; a finely pulverized1,6-GPS-enriched mixture is dissolved therein; after cooling to 70° C.,acid and flavor are added and processed into the plastic melt from the1,1-GPM-enriched mixture as a filling in the tapered roller. The fillingis approximately 10-15% of the total candy mass.

The coating of the filled hard caramel is stable with respect toatmospheric water intake (good storage behavior); the filling is liquidand because it lacks maltitol syrup, suitable for diabetics.

EXAMPLE 11

Production of Coated Soft Caramels, wherein the Coating Contains1,1-GPM-enriched Mixture and the Core, 1,6-GPS-enriched Mixture

The recipe for the soft caramel core corresponds to the recipe asdescribed in Example 7.

The recipe for the dragée coating corresponds to the mixture indicatedin Example 3.

The obtained coated soft caramels exhibit an increased storage stabilityand are suitable for diabetics.

EXAMPLE 12

Replacement of Readily Soluble Sugar Substitutes by a 1,6-GPS-enrichedMixture in Chocolate, in Particular, Calorie-reduced Chocolate

Chocolate Bitter chocolate Milk chocolate Recipe of the mixture Cocoamass   45 kg   11 kg 1,6-GPS-enriched mixture (82% 1,6-GPS, 18% 1,1-GPM)  44 kg   39 kg Hazelnut paste   3 kg   3 kg Whole milk powder —   26 kgCocoa butter —   17 kg Sweeteners  0.1 kg  0.1 kg Recipe of the conchingmass Chocolate mixture 92.1 kg 96.1 kg Cocoa butter  7.0 kg  3.0 kgLecithin  0.5 kg  0.5 kg Flavor 1  0.4 kg  0.3 kg Flavor 2 —  0.1 kgProcess technical data Process parameters Mixing time (min) ca. 5 ca. 10Temperature after the mixing ca 37° C. ca 37° C. Roller performance,kg/h-- 1200-1900 1200-1900 preliminary rolling, according to slit widthand length of the roller Roller performance, kg/h--fine 280-300 280-300rolling (1000 mm in length) Conching temperature max. 70° C. max. 60° C.Conching time (h) 24 24

Of course, the 1,6-GPS-enriched mixture is also suitable for theproduction of calorie-reduced chocolate, in which fat substitutes, suchas inulin or polydextrose, are used. Chocolates can be produced whichhave less than 31%, preferably less than 30%, and particularlypreferably, less than 29% fat content.

The use of 1,6-GPS-enriched mixture makes it possible to increase theconching temperature clearly, in comparison to the traditional rawmaterials, due to the low content of water of hydration (<1%). Improvedflow characteristics of the chocolate masses during the processing areproduced. The 1,6-GPS-enriched mixture in accordance with the invention,therefore, makes it possible to provide an improved method for theproduction of chocolate.

EXAMPLE 13

Sensory Analysis of the Sweetening Power of 1,1-GPM- or 1,6-GPS-enriched1,1-GPM/1,6-GPS Mixtures

For the analysis of the sweetening power, a mixture with a ratio of1,1-GPM/1,6-GPS of 6.79:1 was used as the 1,1-GPM-enriched mixture. Amixture with a ratio of 1,6-GPS/1,1-GPM of 4.51:1 was used as the1,6-GPS-enriched mixture.

The mixtures were given to the test persons in the form of aqueoussolutions.

Threshold value determination:

Concentration series 1 (1,1-GPM) of the threshold test

TABLE II Concentration Recognition of the Sample characterization (g/100g) threshold value (%) 220895/1 0 0 220895/2 2 57.14 220895/3 4 14.28220895/B 5 28.57 220895/4 6 0

Concentration series 2 (1,6-GPS) of the threshold test

TABLE III Concentration Recognition of the Sample characterization(g/1000 g) threshold value (%) 220895/5 0 0 220895/6 2 71.43 220895/7 414.28 220895/A 5 14.28 220895/B 6 0

Differentiation Test

In the differentiation test in pairs (duo test), it was revealed that62.5% (5 of 8 test persons) perceived the 1,6-GPS-rich mixture in a 10%concentration as sweeter and 37.5% (3 of 8 test persons), the1,1-GPM-rich mixture.

EXAMPLE 14

Production and Investigation of Hard Caramels in Accordance with theInvention

For the production of various hard caramels, hydrogenated isomaltulose(1) (ISOMALT^(R)) and mixtures (2)-(7), in accordance with the inventionand as listed in Table IV, were used as raw materials (DS: drysubstance).

TABLE IV 1,1-GPM fraction 1,6-GPS fraction Raw Material Designation (%DS) (% DS) Isomalt^(R) (1) 48.6 50.3 Isomalt PU-3, 3/55-F (2) 2 71.43Isomalt PU-1, 9/45-F (3) 23.1 75.1 Isomalt PU-1, 35-F (4) 32.8 65.6Isomalt Pu-3, 3/tt-FK (5) 60.7 38.3 Isomalt PU-1, 9/45-FK (6) 72.4 26.8Isomalt PU-1/35-FK (7) 83.2 16.4 Key: 1 Raw material designation 21,1-GPM fraction (% DS) 3 1,6-GPS fraction (% DS)

The caramels were stored for different periods of time at 70% relativehumidity at 25° C. (water content of the caramels: 1.5%).

FIG. 10 shows that the hard caramels from traditional hydrogenatedisomaltulose exhibit a considerably increased water intake in thestorage test, in comparison to the products in accordance with theinvention. The caramels in accordance with the invention, therefore,have a considerably better storage capacity.

What is claimed is:
 1. Coated food products, comprising a core and acoating, wherein the coating contains at least one layer comprising1,6-GPS (6-O-α-D-glucopyranosyl-D-sorbitol) and 1,1-GPM(1-O-α-D-glucopyranosyl-D-mannitol) wherein the ratio of 1,6-GPS to1,1GPM is higher than 57:43 and up to 99:1.
 2. Coated products accordingto claim 1, wherein at least 25-45 layers of the coating are present. 3.Coated products according to claim 2 wherein dye is contained in thecoating.
 4. Coated products according to claim 3 wherein the dye istitanium dioxide.
 5. Coated products according to claim 2 wherein thecoating also contains gum arabic in a quantity of 0.5-10 wt %, based onthe dry substance of the coating.
 6. Coated products according to claim2 wherein the coating is 10-90 wt % of the coated product.
 7. Coatedproducts according to claim 6 wherein the coating contains a dye, atleast one sweetener selected from the group consisting of xylitol,mannitol, sorbitol, maltitol, lactitol, erythritol, cyclamate,saccharin, aspartame, glycyrrhizin, neohesperidin, dihydrochalcone,thaumatin, monellin, acesulfame, alitame and sucralose, at least onefiller selected from the group consisting of polydextrose, inulin andcalcium carbonate, at least one polysorbate surfactant, and at least onefilm forming agent selected from the group consisting ofcarboxymethylcellulose, methyl cellulose, gelatin, hydroxypropylcellulose, hydroxyethyl cellulose and ethyl cellulose.
 8. Coatedproducts according to claim 7 wherein the coating also contains gumarabic in a quantity of 0.5-10 wt %, based on the dry substance of thecoating.
 9. Coated products according to claim 2 wherein the coating is25-35 wt % of the coated product.
 10. Coated products according to claim2 wherein the outermost layer of the coating contains at least 57% ofthe 1,6-GPS.
 11. Coated products according to claim 1 wherein thecoating also contains gum arabic in a quantity of 0.5-10 wt %, based onthe dry substance of the coating.
 12. Coated products according to claim1 wherein the coating is 10-90 wt % of the coated product.
 13. Coatedproducts according to claim 12 wherein the coating contains a dye, atleast one sweetener selected from the group consisting of xylitol,mannitol, sorbitol, maltitol, lactitol, erythritol, cyclamate,saccharin, aspartame, glycyrrhizin, neohesperidin, dihydrochalcone,thaumatin, monellin, acesulfame, alitame and sucralose, at least onefiller selected from the group consisting of polydextrose, inulin andcalcium carbonate, at least one polysorbate surfactant and at least onefilm forming agent selected from the group consisting ofcarboxymethylcellulose, methyl cellulose, gelatin, hydroxypropylcellulose, hydroxyethyl cellulose and ethyl cellulose.
 14. Coatedproducts according to claim 13 wherein the coating also contains gumarabic in a quantity of 0.5-10 wt %, based on the dry substance of thecoating.
 15. Coated products according to claim 1 wherein (a) one ormore sugar substitutes selected from the group consisting of xylitol,mannitol, sorbitol, maltitol, lactitol, and erythritol, and (b) a fillerselected from the group consisting of polydextrose, inulin, and calciumcarbonate, or (c) both (a) and (b) are contained in the coating. 16.Coated products according to claim 1 wherein the coating contains (a) apolysorbate surfactant or (b) a film-forming agent selected from thegroup consisting of carboxymethyl cellulose, methycellulose, gelatin,hydroxypropyl cellulose, hydroxyethylcellulose, and ethylcellulose or(c) both (a) and (b).
 17. Coated products according to claim 1 whereinthe core is selected from the group consisting of a chewing gum cushion,a chewing gum ball, a fruit, nut, bean-shaped chocolate, hard caramel,soft caramel, jelly, gum arabic product, nonpareil, a small sugar beadand a snack.
 18. A coated product according to claim 1 wherein theproduct contains gelatin, fat, or fat substitutes.
 19. A coated productaccording to claim 1 which contains intensive sweeteners selected fromthe group consisting of cyclamate, saccharin, aspartame, glycyrrhizin,neohesperidin, dihydrochalcone, thaumatin, monellin, acesulfame, alitameand sucralose.
 20. A coated product according to claim 1 wherein saidproduct is a hard caramel, soft caramel, gelatin product, chocolate,chocolate kiss, chewing gum cushion, ice cream, fruit preparation,chewing gum strip, foam sugar goods or baked goods.
 21. Coated productsaccording to claim 1 in the form of a chewing gum.
 22. The combinationof chocolate and an enriched mixture consisting of 1,6-GPS(6-O-α-D-glucopyranosyl-D-sorbitol) and 1,1-GPM(1-O-α-D-glucopyranosyl-D-mannitol) in which the 1,6-GPS is more than57% up to 99 wt % of said mixture.